CN118032733A - Quick detection method and system for molecular information - Google Patents
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Abstract
The invention provides a method and a system for quickly detecting molecular information, which relate to the technical field of magnetic resonance measurement, and the method comprises the following steps: irradiating the sample to be detected by using laser so as to polarize and read out the electronic state of the nitrogen vacancy color center sensor in the sample to be detected and obtain a fluorescent signal, wherein the sample to be detected also comprises molecules to be detected; applying off-resonance microwaves to the sample to be detected so as to enable the nitrogen vacancy color center sensor and the molecule to be detected to generate resonance; and processing the fluorescent signal by using a fluorescent signal processing module to obtain molecular information of the molecules to be detected. The system comprises: the device comprises a sample module, a laser module, a microwave module and a fluorescence signal processing module.
Description
Technical Field
The invention relates to the technical field of magnetic resonance measurement, in particular to a method and a system for quickly detecting molecular information.
Background
The nitrogen vacancy colour centre (nitrogen VACANCY CENTER, NV colour centre) in diamond is a point defect in diamond with good optical properties and unique energy level structure. The NV color center is widely used in an Optical Detection Magnetic Resonance (ODMR) technology, that is, an electron spin of the NV color center is controlled based on an optical means, and a spin state of the electrons of the NV color center is obtained by detecting fluorescence thereof. Since the spin state of the NV color center electrons is highly sensitive to external magnetic signals, the NV color center can be used for detecting other electron spin signals around the NV color center, namely measuring the electron paramagnetic resonance spectrum of the external environment.
For the past two decades, photo-detection magnetic resonance techniques based on diamond NV colour centers have been widely used in the field of quantum sensing, applications including micro-scale magnetic imaging, weak magnetic measurements, etc. In many applications of the NV colour centre, electron paramagnetic resonance is one of the directions of the most attractive forces. The electron paramagnetic resonance technology is a multifunctional nondestructive analysis technology and has important application value in the research of biological and chemical reaction mechanisms, such as oxidation-reduction reaction, diradical and triplet molecules, reaction kinetics, molecular biology and the like.
However, most of the existing electron paramagnetic resonance applications based on the diamond NV color center are based on detecting electron paramagnetic resonance signals of single molecules by single NV color center. This detection mode has great difficulty and instability. On one hand, the fluorescence signal of a single NV color center is weak, so that the speed of accumulating signals is low, and the detection efficiency is limited; on the other hand, the charge state of a single NV color center as the near surface of the sensor becomes unstable under long-term illumination, thereby affecting the performance of the sensor itself, and furthermore, many kinds of radicals also have a phenomenon of signal quenching during detection, which is also caused by laser irradiation of high power density. Thus, detection of an electron paramagnetic resonance signal of a single molecule using a single NV color center typically takes hours or even days, and it is difficult to stably detect an electron paramagnetic resonance signal of a target molecule in most cases.
Disclosure of Invention
In view of the above problems, the present invention provides a method and a system for rapid detection of molecular information.
According to a first aspect of the present invention, there is provided a method for rapid detection of molecular information, comprising: irradiating the sample to be detected by using laser so as to polarize and read out the electronic state of the nitrogen vacancy color center sensor in the sample to be detected and obtain a fluorescent signal, wherein the sample to be detected also comprises molecules to be detected; applying off-resonance microwaves to the sample to be detected so as to enable the nitrogen vacancy color center sensor and the molecule to be detected to generate resonance; and processing the fluorescent signal by using a fluorescent signal processing module to obtain molecular information of the molecules to be detected.
According to an embodiment of the present invention, the method for rapidly detecting molecular information further includes: and uniformly dispersing the molecules to be detected on the surface of the diamond comprising the nitrogen vacancy color center sensor to obtain a sample to be detected.
According to an embodiment of the present invention, irradiating a sample to be measured with laser light so as to polarize and read out an electronic state of a nitrogen-vacancy color center sensor in the sample to be measured includes: irradiating a sample to be measured based on a laser corresponding to a target laser power, the target laser power being obtained according to the following manner: and adjusting the initial laser power of laser irradiating the sample to be measured until the electron polarization duration of the nitrogen vacancy color center sensor reaches the preset target electron polarization duration, so as to obtain the target laser power.
According to an embodiment of the invention, the fluorescence signal comprises an accumulated fluorescence signal obtained after repeated measurement for a plurality of times; the method for obtaining the molecular information of the sample to be detected by utilizing the fluorescence signal processing module to process the fluorescence signal comprises the following steps: processing the accumulated fluorescence signal by using a fluorescence signal processing module to obtain an electron paramagnetic resonance spectrum related to the sample to be detected; and processing the electron paramagnetic resonance spectrum by using a fluorescent signal processing module to obtain molecular information corresponding to the molecules to be detected.
According to an embodiment of the present invention, processing the fluorescent signal with the fluorescent signal processing module to obtain the electron paramagnetic resonance spectrum includes: recording the intensity of a fluorescent signal corresponding to each frequency of the off-resonance microwaves by using a fluorescent signal processing module; and obtaining an electron paramagnetic resonance spectrum taking the frequency of the off-resonance microwave as a horizontal axis and the intensity of the fluorescence signal as a vertical axis according to the frequency of the off-resonance microwave and the intensity of the corresponding fluorescence signal.
According to an embodiment of the present invention, the molecular information includes molecular energy level information, molecular species information, and molecular motion information; processing the electron paramagnetic resonance spectrum by using a fluorescent signal processing module to obtain molecular information corresponding to the molecules to be detected, wherein the method comprises the following steps of: and determining the molecular energy level information, the kind information and the motion information according to the number, the position, the intensity and the broadening of the spectrum peaks of the electron paramagnetic resonance spectrum.
According to a second aspect of the present invention, there is provided a molecular information rapid detection system comprising: the sample module is used for placing a sample to be measured and adjusting the position of the sample to be measured; the laser module is used for irradiating the sample to be detected by utilizing laser so as to polarize and read out the electronic state of the nitrogen vacancy color center sensor in the sample to be detected, obtain a fluorescent signal, and the sample to be detected also comprises molecules to be detected; the microwave module is used for applying off-resonance microwaves to the sample to be detected so as to enable the nitrogen vacancy color center sensor and the molecule to be detected to generate resonance; and the fluorescence signal processing module is used for processing the fluorescence signal by utilizing the fluorescence signal processing module to obtain the molecular information of the molecules to be detected.
According to an embodiment of the present invention, a laser module includes: a laser source configured to emit an initial laser light; the convex lens is configured to receive the initial laser and focus the initial laser to obtain laser; a dichroic mirror configured to reflect laser light and transmit the fluorescent signal; and the objective lens is configured to receive the laser light reflected by the bi-directional mirror and transmit the laser light to the sample module, and collect fluorescent signals emitted by the sample module.
According to an embodiment of the present invention, a fluorescent signal processing module includes: the fluorescence signal collecting and detecting assembly is used for recording the intensity of the fluorescence signal corresponding to each frequency of the off-resonance microwaves; and the computer is used for obtaining an electron paramagnetic resonance spectrum taking the frequency of the off-resonance microwave as a horizontal axis and the intensity of the fluorescence signal as a vertical axis according to the frequency of the off-resonance microwave and the intensity of the corresponding fluorescence signal.
According to an embodiment of the invention, a microwave module includes: a microwave source configured to emit an initial off-resonance microwave; the microwave amplifier is configured to receive the initial off-resonance microwaves and amplify the initial off-resonance microwaves to obtain off-resonance microwaves; the sample module includes: a displacement table configured to place a sample to be measured and adjust a position of the sample to be measured; and the microwave radiation assembly is configured to receive off-resonance microwaves emitted by the microwave module and apply the off-resonance microwaves to the sample to be tested.
According to the embodiment of the invention, the molecular information is rapidly detected by a mode of parallel detection of a large number of nitrogen vacancy color center sensors, so that the detection efficiency and stability are effectively improved, and the problems of slower signal accumulation speed and limited detection efficiency caused by weaker fluorescent signals of single nitrogen vacancy color centers are avoided; and off-resonance microwaves are applied to the sample to be measured under the condition of zero magnetic field, so that the electron spin orientation of the molecule to be measured can not influence the position of a spectral line signal peak, the spectral line broadening and distortion caused by the electron spin orientation distribution of the molecule to be measured are avoided, and meanwhile, the limitation of microwave radiation field uniformity on wide-field measurement is solved to a great extent because complicated microwave pulse operation is not needed.
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The foregoing and other objects, features and advantages of the invention will be apparent from the following description of embodiments of the invention with reference to the accompanying drawings, in which:
FIG. 1 shows a flow chart of a method for rapid detection of molecular information according to an embodiment of the invention;
FIG. 2 shows a schematic diagram of electron paramagnetic resonance spectra of 14 N-TEMPO according to an embodiment of the invention;
FIG. 3 shows a schematic diagram of electron paramagnetic resonance spectra of 15 N-TEMPO according to an embodiment of the invention;
FIG. 4 shows a block diagram of a molecular information rapid detection system according to an embodiment of the present invention;
Fig. 5 shows a schematic diagram of a molecular information rapid detection system according to an embodiment of the invention.
Detailed Description
For the following, embodiments of the present invention will be described with reference to the drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It should be noted that the terms used herein should be construed to have meanings consistent with the context of the present specification and should not be construed in an idealized or overly formal manner.
Where a convention analogous to "at least one of A, B and C, etc." is used, in general such a convention should be interpreted in accordance with the meaning of one of skill in the art having generally understood the convention (e.g., "a system having at least one of A, B and C" would include, but not be limited to, systems having a alone, B alone, C alone, a and B together, a and C together, B and C together, and/or A, B, C together, etc.).
The fluorescence signal of a single nitrogen vacancy color center is weaker, so that the signal accumulation speed is slower, and the detection efficiency is limited; on the other hand, the charge state of a single nitrogen-vacancy color center as the near surface of the sensor may become unstable under long-term illumination, thereby affecting the performance of the sensor itself.
The inventor finds that spin signals of a large number of molecules to be detected can be detected in parallel by using a large number of nitrogen-vacancy color center sensors, and the spin signals are configured under the zero magnetic field condition, so that all the molecules to be detected with different orientations have the same energy level cleavage, and can be detected by the nitrogen-vacancy color center sensors at the same time.
In view of this, the embodiment of the invention provides a method for rapidly detecting molecular information, which uses laser to polarize and read out a nitrogen vacancy color center sensor so as to polarize and read out the electronic state of the nitrogen vacancy color center sensor and obtain a fluorescence signal; applying off-resonance microwaves to the prepared sample to be detected so as to enable the equivalent energy level of the nitrogen vacancy color center sensor and the spin energy level of the molecule to be detected to generate resonance; and processing the fluorescent signal by using a fluorescent signal processing module to obtain the molecular information of the sample to be detected.
Fig. 1 shows a flowchart of a method for rapid detection of molecular information according to an embodiment of the present invention.
As shown in fig. 1, the molecular information rapid detection method includes operations S110 to S130:
In operation S110, the sample to be measured is irradiated with laser light so as to polarize and read out the electronic state of the nitrogen-vacancy color center sensor in the sample to be measured, thereby obtaining a fluorescent signal, and the sample to be measured further includes the molecule to be measured.
In operation S120, off-resonance microwaves are applied to the sample to be measured so as to resonate the nitrogen-vacancy color center sensor with the molecule to be measured.
In operation S130, the fluorescence signal processing module is used to process the fluorescence signal, so as to obtain the molecular information of the molecule to be detected.
According to embodiments of the present invention, the nitrogen-vacancy colour-core sensor has good optical properties and unique energy level structure due to a point defect in diamond. The nitrogen vacancy color center spin of the nitrogen vacancy color center sensor can meet the magnetic detection requirements of high sensitivity and high spatial resolution simultaneously, and has the characteristics of small volume, long spin coherence time, large working temperature range, high stability and quick starting time.
According to the embodiment of the invention, the sample to be measured is irradiated by laser, and the electron state of the nitrogen vacancy color center is excited to make the transition between the ground state and the excited state until the sample to be measured is polarized to a specific spin state, namely a bright state.
According to embodiments of the present invention, the intensity of the fluorescence signal generated by the nitrogen-vacancy color-center sensor in the bright state is stronger relative to the dark state.
According to an embodiment of the present invention, the off-resonance microwave intensity Ω is proportional to the off-resonance amount of the zero-field cleavage of the nitrogen-vacancy color center, and the proportionality coefficient is κ=0.3, i.e. Ω/Δ=κ=0.3. For example, if the sample to be tested is scanned at a frequency of 2910 MHz to 3020 to MHz, the corresponding off-resonance microwave intensity should be 12 MHz to 45 MHz. The intensity of the off-resonance microwaves on the sample to be measured is calibrated by nitrogen vacancy color-centered ratio oscillation. For example, when the frequency of the microwaves applied to the nitrogen-vacancy toner is 2870 MHz and the power is 30 dBm, the ratio of the oscillation frequency measured by the nitrogen-vacancy toner sensor is 30 MHz, i.e. the intensity of the microwaves on the sample to be measured is 30 MHz. The calibration means that the applied microwave power is 30 dBm in the actual frequency sweeping range of 2720 MHz-3020 and MHz, namely, the corresponding microwave intensity on the sample to be measured is 30 MHz.
According to the embodiment of the invention, under the action of off-resonance microwaves with off-resonance quantity delta, the nitrogen vacancy color center generates the splitting with the equivalent energy level approximately equal to delta under the rotation coordinate system, and the spin energy level of the molecule to be detected has the energy level difference omega. When the frequency of the off-resonance microwaves satisfies the off-resonance condition, i.e., when Δ is approximately equal to ω, the cleavage of the nitrogen-vacancy color center equivalent energy level is the same as the energy level difference of the spin energy level of the molecule to be measured, and therefore, the nitrogen-vacancy color center sensor and the molecule to be measured can resonate. When the nitrogen-vacancy color center sensor and the molecule to be detected generate resonance, the intensity of a fluorescent signal generated by the nitrogen-vacancy color center changes along with the resonance.
According to the embodiment of the invention, all molecules to be detected with different orientations have the same energy level cleavage under the zero magnetic field, so that the molecules to be detected can be detected by a large number of nitrogen vacancy color center sensors at the same time, and therefore, compared with the traditional electron spin detection method (such as double electron-electron resonance) based on the nitrogen vacancy color center, the embodiment of the invention avoids the problems of spectral line broadening and distortion caused by electron spin orientation distribution of the molecules to be detected, can realize wide-field parallel acceleration, and further realize rapid molecular information detection.
According to the embodiment of the invention, off-resonance microwaves are applied to the sample to be detected, under the action of the off-resonance microwaves, the nitrogen vacancy color center sensor in the sample to be detected turns over the electronic state of the nitrogen vacancy color center under the action of the off-resonance microwaves, and the proportion of the bright state electrons and the dark state electrons changes, so that the intensity of a fluorescent signal changes. That is, when the nitrogen-vacancy color center sensor and the molecule to be measured resonate, the intensity of the fluorescent signal generated by the nitrogen-vacancy color center changes with the resonance.
According to the embodiment of the invention, the molecular information is rapidly detected by a mode of parallel detection of a large number of nitrogen vacancy color center sensors, so that the detection efficiency and stability are effectively improved, and the problems of slower signal accumulation speed and limited detection efficiency caused by weaker fluorescent signals of single nitrogen vacancy color centers are avoided; and off-resonance microwaves are applied to the sample to be measured under the condition of zero magnetic field, so that the electron spin orientation of the molecule to be measured can not influence the position of a spectral line signal peak, the spectral line broadening and distortion caused by the electron spin orientation distribution of the molecule to be measured are avoided, and meanwhile, the limitation of microwave radiation field uniformity on wide-field measurement is solved to a great extent because complicated microwave pulse operation is not needed.
According to an embodiment of the present invention, the method for rapidly detecting molecular information further includes: and uniformly dispersing a large number of molecules to be measured on the surface of the diamond comprising a large number of nitrogen vacancy color center sensors to obtain a sample to be measured.
According to an embodiment of the present invention, tetramethyl piperidine oxide (TEMPO) free radical was dissolved in acetone (liquid phase solvent) and mixed with 1% volume fraction of polymethyl methacrylate (PMMA) toluene solution (solid dispersion) such that the final TEMPO concentration in PMMA solids was 100 mM. The mixed solution is fixed on the surface of diamond comprising a plurality of nitrogen vacancy color center sensors in a spin coating mode, and the spin coating rotating speed can be 4800 rpm. The invention is not limited to the choice of solid dispersant and liquid phase solvent, and can be chosen by the person skilled in the art according to the actual needs.
According to the embodiment of the invention, the mixed solution containing the molecules to be detected is spin-coated on the surface of the diamond comprising a large number of nitrogen vacancy color center sensors, so that the number of the molecules to be detected and the number of the nitrogen vacancy color center sensors are effectively increased, and therefore, enough signal-to-noise ratio accumulation is completed within a time scale of sub-minute or even second order, high-efficiency extraction of molecular information can be realized, and the problems of slower accumulation signal speed and limited detection efficiency caused by weaker fluorescent signals of single nitrogen vacancy color center are avoided.
According to an embodiment of the present invention, irradiating a sample to be measured with laser light so as to polarize and read out an electronic state of a nitrogen-vacancy color center sensor in the sample to be measured includes: irradiating a sample to be measured based on a laser corresponding to a target laser power, the target laser power being obtained according to the following manner: and adjusting the initial laser power of laser irradiating the sample to be measured until the electron polarization duration of the nitrogen vacancy color center sensor reaches the preset target electron polarization duration, so as to obtain the target laser power.
According to an embodiment of the invention, the relaxation time of the nitrogen-vacancy colour-core sensor isThe corresponding polarization rate is/>In order to obtain the target polarization duration, the nitrogen-vacancy color center sensor needs to reach the optimal polarization rate, so that the initial laser power of the laser irradiating the sample to be measured is adjusted until the electron polarization duration of the nitrogen-vacancy color center sensor reaches the preset target electron polarization duration, and the target laser power is obtained. When the laser power is 80uW, the optimal polarization rate isReach the target polarization duration/>I.e. 330us, and thus the target laser power is 80uW.
According to the embodiment of the invention, detection of electron paramagnetic resonance spectrum of a molecule to be detected is realized based on a nitrogen vacancy color center sensor, and the nitrogen vacancy color center has good optical properties and unique energy level structure and specifically comprises the following steps: the electron spin state of the nitrogen vacancy colour centre can be polarised by a 532nm laser to a specific electron state; the nitrogen vacancy color centers in different electronic states have different fluorescence intensities under 532nm laser irradiation; further, by adjusting the laser power, when the target laser power is 80uW, the polarization rate of the electron state of the nitrogen vacancy color center polarized to a specific electron state reaches the optimum.
According to the embodiment of the invention, the electron polarization duration of the nitrogen-vacancy color center sensor reaches the target polarization duration by adjusting the laser power, so that the molecular information detection rate can be effectively improved.
According to an embodiment of the invention, the fluorescence signal comprises an accumulated fluorescence signal obtained after repeated measurement for a plurality of times; the method for obtaining the molecular information of the sample to be detected by utilizing the fluorescence signal processing module to process the fluorescence signal comprises the following steps: processing the accumulated fluorescence signal by using a fluorescence signal processing module to obtain an electron paramagnetic resonance spectrum related to the sample to be detected; and processing the electron paramagnetic resonance spectrum by using a fluorescent signal processing module to obtain molecular information corresponding to the molecules to be detected.
According to the embodiment of the invention, off-resonance microwaves are applied to the sample to be detected, and under the action of the off-resonance microwaves, the electronic state of the nitrogen vacancy color center sensor in the sample to be detected can be overturned, namely the proportion of bright-state electrons and dark-state electrons is changed, so that the intensity of a fluorescent signal is changed. When the nitrogen-vacancy color center sensor and the molecule to be detected generate resonance, the intensity of a fluorescent signal generated by the nitrogen-vacancy color center changes along with the resonance. When the off-resonance microwaves are scanned within a certain frequency range, the fluorescence signal processing module records the fluorescence signal intensity corresponding to each frequency, and performs accumulated acquisition to obtain a spectrogram taking the frequency of the off-resonance microwaves as a horizontal axis and the intensity of the fluorescence signal as a vertical axis, namely an electron paramagnetic resonance spectrum. And the fluorescence signal processing module further determines molecular information of the molecules to be detected according to the attribute of the electron paramagnetic resonance spectrum.
According to the embodiment of the invention, the nitrogen vacancy color center sensor and the molecules to be measured are driven by continuously applying off-resonance microwaves, so that complex microwave pulse control is avoided, and the limitation of microwave radiation field uniformity on wide-field measurement is solved to a great extent. Therefore, the embodiment of the invention utilizes all nitrogen vacancy color centers in the light spot with the diameter of 16um to detect all target molecules in the range in parallel, thereby realizing the effect of wide-field parallel acceleration. And then enough accumulation of fluorescent signals can be obtained in the time of subminute or even second order, and the electron paramagnetic resonance spectrum of the target molecule can be obtained. Compared with the traditional method, the efficiency of obtaining the molecular information determined by the electron paramagnetic resonance spectrum is obviously improved.
According to an embodiment of the present invention, processing the fluorescent signal with the fluorescent signal processing module to obtain the electron paramagnetic resonance spectrum includes: recording the intensity of a fluorescent signal corresponding to each frequency of the off-resonance microwaves by using a fluorescent signal processing module; and obtaining an electron paramagnetic resonance spectrum taking the frequency of the off-resonance microwave as a horizontal axis and the intensity of the fluorescence signal as a vertical axis according to the frequency of the off-resonance microwave and the intensity of the corresponding fluorescence signal.
According to the embodiment of the invention, off-resonance microwaves are scanned in a range of intervals, at the moment, bright-state electrons and dark-state electrons of the nitrogen-vacancy color center sensor are driven by the off-resonance microwaves with different frequencies and can turn over to different proportions of electronic states, so that the fluorescence intensity is changed, and the fluorescence signal processing module is used for recording the intensity of a fluorescence signal corresponding to each frequency of the off-resonance microwaves; and obtaining an electron paramagnetic resonance spectrum taking the frequency of the off-resonance microwave as a horizontal axis and the intensity of the fluorescence signal as a vertical axis according to the frequency of the off-resonance microwave and the intensity of the corresponding fluorescence signal.
According to an embodiment of the present invention, the molecular information includes molecular energy level information, molecular species information, and molecular motion information.
According to the embodiment of the invention, the electron paramagnetic resonance spectrum is processed by the fluorescent signal processing module, and the obtaining of the molecular information corresponding to the molecules to be detected comprises determining the molecular energy level information, the kind information and the movement information according to the number, the position, the intensity and the stretching of the spectrum peaks of the electron paramagnetic resonance spectrum. According to the embodiment of the invention, the free radical nuclear spin number of the molecule to be detected can be analyzed and judged according to the number and the intensity of the spectrum peaks of the electron paramagnetic resonance spectrum, so that the Hamiltonian quantity of the molecule to be detected can be obtained, wherein the Hamiltonian quantity contains the hyperfine coupling constant of the molecule to be detected; the corresponding relation between the theoretical value of the spectral peak position of the electron paramagnetic resonance spectrum and the hyperfine coupling constant of the molecule to be detected can be obtained by solving the eigenvalue of the Hamiltonian, the hyperfine coupling constant of the molecule to be detected can be obtained by calculating the actual position of the spectral peak of the electron paramagnetic resonance spectrum measured by combining experiments, and the molecular energy level information and the molecular type information of the molecule to be detected can be obtained according to the hyperfine coupling constant of the molecule to be detected.
According to the embodiment of the invention, the spectral line broadening and intensity of the electron paramagnetic resonance spectrum reflect the molecular motion information of the molecules to be detected, and the molecules to be detected need to be analyzed according to specific spectral lines.
According to the embodiment of the invention, the sample to be detected is irradiated by laser, and the electron state of the nitrogen-vacancy color center sensor is polarized to a specific spin state; applying off-resonance microwaves to the sample to be detected, so that the equivalent energy level splitting of the nitrogen vacancy color center under a rotating coordinate system is matched with the energy level difference of the molecule to be detected, and further generating fluorescent signals with different intensities; the fluorescence signal processing module records the fluorescence signal intensity of the nitrogen vacancy color center sensor under the drive of off-resonance microwaves with different frequencies to obtain an electron paramagnetic resonance spectrum; and determining the molecular information of the molecules to be detected through electron paramagnetic resonance spectroscopy.
According to the embodiment of the invention, a sample to be measured is irradiated by laser, the sample to be measured can be prepared by spin coating a solid dispersion mixed solution containing TEMPO free radicals on the surface of diamond comprising a large number of nitrogen vacancy color center sensors, and under the irradiation of 532nm laser with the power of 80uW, the electronic state of the nitrogen vacancy color center sensor is transited to a bright state within the target polarization duration to obtain a high-intensity fluorescent signal; applying 2720 MHz-3020 MHz off-resonance microwaves to a sample to be detected, so that the equivalent energy level splitting of the nitrogen vacancy color center under a rotating coordinate system is matched with the energy level difference of molecules to be detected, and further fluorescent signals with different intensities are generated; recording the intensity of a fluorescent signal corresponding to each frequency of the off-resonance microwaves by using a fluorescent signal processing module; according to the frequency of the off-resonance microwave and the intensity of the corresponding fluorescent signal, an electron paramagnetic resonance spectrum with the frequency of the off-resonance microwave as a horizontal axis and the intensity of the fluorescent signal as a vertical axis is obtained; and determining the molecular energy level information, the molecular type information and the molecular motion information of the molecules to be detected through an electron paramagnetic resonance spectrum.
FIG. 2 shows a schematic diagram of electron paramagnetic resonance spectra of 14N-TEMPO according to an embodiment of the invention; FIG. 3 shows a schematic diagram of electron paramagnetic resonance spectra of 15N-TEMPO according to an embodiment of the invention.
According to the embodiment of the invention, the electron paramagnetic resonance spectrum obtained by the molecular information rapid detection method is shown in fig. 2 and 3, has higher spectral line resolution, avoids the problems of spectral line broadening and distortion caused by the distribution of the target electron spin orientation, and can obtain more accurate molecular information.
According to the embodiment of the invention, the detection efficiency and stability of molecular information detection are remarkably improved based on the molecular information rapid detection method. A large number of electron spins to be measured (corresponding to 10 8 electron spins within a thickness of 10 nm) are detected in parallel with a large number of nitrogen vacancy colour centers (10 5) so that sufficient signal-to-noise ratio accumulation is achieved in a time scale of the order of minutes or even seconds.
According to the embodiment of the invention, based on the molecular information rapid detection method, off-resonance microwaves are applied to the nitrogen vacancy color center sensor and the molecules to be detected under the condition of zero magnetic field, and the electron spin orientation of the molecules to be detected does not influence the position of a spectral line signal peak. Therefore, the method has higher spectral line resolution, and avoids the spectral line broadening and distortion caused by the electron spin orientation distribution of the molecules to be detected. In contrast, the position of the spectral line resonance peak measured by the conventional electron spin detection method (for example, dual electron-electron resonance) based on the nitrogen vacancy color center depends on the included angle of the target electron spin orientation with the nitrogen vacancy color center axis. Therefore, the quick detection method based on the molecular information of the invention enables the resonance condition of the nitrogen vacancy color center sensor and the spin of the molecule to be detected not to depend on the angle any more.
According to the embodiment of the invention, the molecular information rapid detection method is based on the fact that the off-resonance microwaves are continuously applied to drive the nitrogen vacancy color center sensor and the molecules to be detected, complicated microwave pulse control is not needed, and the limitation of microwave radiation field uniformity on wide-field measurement is solved to a great extent.
FIG. 4 is a block diagram showing a molecular information rapid detection system according to an embodiment of the present invention
As shown in fig. 4, an embodiment of the present invention further provides a rapid molecular information detection system 300, which includes a sample module 310, a laser module 320, a microwave module 330, and a fluorescent signal processing module 340.
The sample module 310 is used for placing a sample to be measured and adjusting the position of the sample to be measured.
The laser module 320 is used for irradiating the sample to be measured with laser light so as to polarize and read out the electronic state of the nitrogen vacancy color center sensor in the sample to be measured, and obtain a fluorescence signal, wherein the sample to be measured also comprises molecules to be measured.
The microwave module 330 is configured to apply off-resonance microwaves to the sample to be measured, so as to resonate the nitrogen-vacancy color center sensor with the molecule to be measured.
The fluorescence signal processing module 340 is configured to process the fluorescence signal to obtain molecular information of the molecule to be detected.
According to the embodiment of the invention, the molecular information is rapidly detected by a mode of parallel detection of a large number of nitrogen vacancy color center sensors, so that the detection efficiency and stability are effectively improved, and the problems of slower signal accumulation speed and limited detection efficiency caused by weaker fluorescent signals of single nitrogen vacancy color centers are avoided; and off-resonance microwaves are applied to the sample to be measured under the condition of zero magnetic field, so that the electron spin orientation of the molecule to be measured does not influence the position of a spectral line signal peak, the spectral line broadening and distortion caused by the electron spin orientation distribution of the molecule to be measured are avoided, and meanwhile, the limitation of microwave radiation field uniformity on wide-field measurement is solved to a great extent because complicated microwave pulse operation is not needed.
Fig. 5 shows a schematic diagram of a molecular information rapid detection system according to an embodiment of the invention.
As shown in fig. 5, the molecular information rapid detection system 300 includes a sample module 310, a laser module 320, a microwave module 330, and a fluorescent signal processing module 340.
The sample module 310 includes a displacement stage 311 and a microwave radiation assembly 312.
The laser module 320 includes a laser source 321, a convex lens 322, a dichroic mirror 323, and an objective lens 324.
The microwave module 330 includes a microwave source 331 and a microwave amplifier 332.
The fluorescence signal processing module 340 includes a fluorescence signal collection detection assembly 341 and a computer 342.
As shown in fig. 5, the laser source 321 is configured to emit an initial laser light.
The convex lens 322 is configured to receive the initial laser light, and focus the initial laser light to obtain laser light.
The dichroic mirror 323 is configured to reflect laser light and transmit a fluorescent signal.
The objective lens 324 is configured to receive the laser light reflected by the dichroic mirror 323 and emit the laser light to the sample module while collecting the fluorescent signal emitted from the sample module.
According to an embodiment of the present invention, the position of the convex lens 322 is adjusted so that the beam emitted by the objective lens 324 is a collimated beam with a full width half maximum of 16 um, so as to implement wide-field excitation, wherein the number of color centers contained in the size range of the collimated beam is about 10 5.
According to the embodiment of the invention, the initial laser power is adjusted by adjusting the attenuation coefficient of the laser source 321, so that the electronic polarization duration of the nitrogen-vacancy color center sensor reaches the target polarization duration, and the molecular information detection rate can be effectively improved.
According to the embodiment of the present invention, the dichroic mirror 323 can reflect the laser light to the objective lens 324 and transmit the fluorescent signal output by the objective lens 324, so that the fluorescent signal can be received by the fluorescent signal processing module 340.
As shown in fig. 5, the fluorescence signal collection probe assembly 341 is configured to record the intensity of the fluorescence signal corresponding to each frequency of the off-resonance microwaves.
The computer 342 is configured to obtain an electron paramagnetic resonance spectrum with the frequency of the off-resonance microwave as the horizontal axis and the intensity of the fluorescence signal as the vertical axis according to the frequency of the off-resonance microwave and the intensity of the fluorescence signal.
According to the embodiment of the invention, the fluorescence signal collection and detection component 341 is used for collecting the fluorescence signal generated by the nitrogen vacancy color center sensor in the off-resonance microwave frequency sweeping process, and the fluorescence count collected by the avalanche diode of the fluorescence signal collection and detection component 341 is about 4-5 Mcps and is just close to the maximum value of the linear interval of the fluorescence signal.
According to the embodiment of the invention, the computer 342 is utilized to accumulate fluorescence, and an electron paramagnetic resonance spectrum of the molecule to be detected can be obtained within a sub-minute time, wherein the off-resonance of the spectrum peak of the electron paramagnetic resonance spectrum is +/-95 MHz, the longitudinal ultra-fine coupling constant of the TEMPO free radical can be extracted, and the molecular energy level information and the molecular type information of the TEMPO free radical can be obtained according to the longitudinal ultra-fine coupling constant.
As shown in fig. 5, the microwave source 331 is configured to emit an initial off-resonance microwave.
The microwave amplifier 332 is configured to receive the initial off-resonant microwave, amplify the initial off-resonant microwave, and obtain the off-resonant microwave.
As shown in fig. 5, the displacement stage 311 is configured to place a sample to be measured and adjust the position of the sample to be measured.
The microwave radiation assembly 312 is configured to receive off-resonance microwaves emitted by the microwave module 330 and to apply off-resonance microwaves to the sample to be measured.
According to the embodiment of the invention, the prepared sample to be tested is fixed on the displacement table 311 and is fixed on a cover glass through ultraviolet glue, and is assembled with the microwave radiation component 312 in a reverse buckling manner.
According to an embodiment of the present invention, the microwave radiation assembly 312 radiates off-resonance microwaves emitted from the microwave amplifier 332 to the nitrogen-vacancy color center sensor, so that the nitrogen-vacancy color center sensor resonates with a molecule to be measured, wherein fluorescent signals can be collected by the objective lens 324 and injected into the fluorescent signal collection detection assembly 341.
As shown in fig. 5, a laser source 321 emits initial laser light, the laser light is focused by a convex lens 322 and reflected into an objective lens 324 through a dichroic mirror 323, and the objective lens 324 emits the laser light to a sample to be measured on a displacement table 311 to generate a fluorescence signal; the microwave source 331 emits initial off-resonance microwaves, the initial off-resonance microwaves are amplified by the microwave amplifier 332 and then emitted to the microwave radiation assembly 312, and the microwave radiation assembly 312 applies the off-resonance microwaves to the sample to be measured on the displacement table 311; the nitrogen vacancy color center sensor in the sample to be detected resonates with the molecule to be detected; the objective lens 324 collects and emits fluorescent signals, the fluorescent signals are collected by the fluorescent signal collection detection component 341 through the bi-directional color mirror 323, and the fluorescent signals are processed by the computer 342 to obtain an electron paramagnetic resonance spectrum, so that molecular information of molecules to be detected is determined according to the electron paramagnetic resonance spectrum.
Those skilled in the art will appreciate that the features recited in the various embodiments of the invention and/or in the claims may be combined in various combinations and/or combinations, even if such combinations or combinations are not explicitly recited in the invention. In particular, the features recited in the various embodiments of the invention and/or in the claims can be combined in various combinations and/or combinations without departing from the spirit and teachings of the invention. All such combinations and/or combinations fall within the scope of the invention.
The embodiments of the present invention are described above. These examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Although the embodiments are described above separately, this does not mean that the measures in the embodiments cannot be used advantageously in combination. The scope of the invention is defined by the appended claims and equivalents thereof. Various alternatives and modifications can be made by those skilled in the art without departing from the scope of the invention, and such alternatives and modifications are intended to fall within the scope of the invention.
Claims (10)
1. A method for rapid detection of molecular information, the method comprising:
irradiating a sample to be detected by using laser so as to polarize and read out the electronic state of a nitrogen vacancy color center sensor in the sample to be detected and obtain a fluorescent signal, wherein the sample to be detected also comprises molecules to be detected which are arranged on the surface of the nitrogen vacancy color center sensor;
Applying off-resonance microwaves to the sample to be measured so as to enable the nitrogen vacancy color center sensor and the molecule to be measured to generate resonance;
And processing the fluorescence signal by utilizing a fluorescence signal processing module to obtain the molecular information of the molecule to be detected.
2. The method according to claim 1, wherein the method further comprises:
and uniformly dispersing the molecules to be detected on the surface of the diamond comprising the nitrogen vacancy color center sensor to obtain the sample to be detected.
3. The method of claim 1, wherein irradiating the sample to be measured with the laser light to facilitate polarizing and reading out the electronic state of the nitrogen-vacancy color-center sensor in the sample to be measured comprises:
Irradiating the sample to be measured based on a laser corresponding to a target laser power, the target laser power being obtained according to:
And adjusting the initial laser power of the laser irradiating the sample to be detected until the electron polarization duration of the nitrogen vacancy color center sensor reaches the preset target electron polarization duration, so as to obtain the target laser power.
4. The method of claim 1, wherein the fluorescence signal comprises an accumulated fluorescence signal obtained after a plurality of repeated measurements;
the method for obtaining the molecular information of the sample to be detected by utilizing the fluorescence signal processing module to process the fluorescence signal comprises the following steps:
Processing the accumulated fluorescence signals by using the fluorescence signal processing module to obtain an electron paramagnetic resonance spectrum related to the sample to be detected;
and processing the electron paramagnetic resonance spectrum by using the fluorescence signal processing module to obtain molecular information corresponding to the molecules to be detected.
5. The method of claim 4, wherein processing the accumulated fluorescence signal with the fluorescence signal processing module yields an electron paramagnetic resonance spectrum associated with the sample to be measured, comprising:
Recording the intensity of the accumulated fluorescence signal corresponding to each frequency of the off-resonance microwaves by using the fluorescence signal processing module;
And obtaining an electron paramagnetic resonance spectrum taking the frequency of the off-resonance microwave as a horizontal axis and the intensity of the accumulated fluorescence signal as a vertical axis according to the frequency of the off-resonance microwave and the intensity of the corresponding accumulated fluorescence signal.
6. The method of claim 4, wherein the molecular information includes molecular energy level information, molecular species information, and molecular motion information;
the processing the electron paramagnetic resonance spectrum by using the fluorescence signal processing module to obtain molecular information corresponding to the molecule to be detected includes:
And determining the molecular energy level information, the kind information and the motion information according to the number, the position, the intensity and the broadening of the spectrum peaks of the electron paramagnetic resonance spectrum.
7. A molecular information rapid detection system for performing the method of any one of claims 1 to 6, the system comprising:
the sample module is used for placing a sample to be measured and adjusting the position of the sample to be measured;
The laser module is used for irradiating a sample to be detected by utilizing laser so as to polarize and read out the electronic state of the nitrogen vacancy color center sensor in the sample to be detected and obtain a fluorescent signal, and the sample to be detected also comprises molecules to be detected;
The microwave module is used for applying off-resonance microwaves to the sample to be detected so as to enable the nitrogen vacancy color center sensor and the molecule to be detected to generate resonance;
and the fluorescence signal processing module is used for processing the fluorescence signal to obtain the molecular information of the molecule to be detected.
8. The system of claim 7, wherein the laser module comprises:
A laser source configured to emit an initial laser light;
The convex lens is configured to receive the initial laser and focus the initial laser to obtain the laser;
A dichroic mirror configured to reflect the laser light and transmit the fluorescent signal;
And an objective lens configured to receive the laser light reflected by the dichroic mirror and to emit the laser light to the sample module while collecting the fluorescent signal emitted from the sample module.
9. The system of claim 7, wherein the fluorescence signal processing module comprises:
the fluorescence signal collecting and detecting assembly is used for recording the intensity of the fluorescence signal corresponding to each frequency of the off-resonance microwaves;
And the computer is used for obtaining an electron paramagnetic resonance spectrum taking the frequency of the off-resonance microwave as a horizontal axis and the intensity of the fluorescence signal as a vertical axis according to the frequency of the off-resonance microwave and the corresponding intensity of the fluorescence signal.
10. The system of claim 7, wherein the system further comprises a controller configured to control the controller,
The microwave module includes:
a microwave source configured to emit an initial off-resonance microwave;
The microwave amplifier is configured to receive the initial off-resonance microwaves and amplify the initial off-resonance microwaves to obtain off-resonance microwaves;
the sample module includes:
a displacement table configured to place a sample to be measured and adjust a position of the sample to be measured;
and the microwave radiation assembly is configured to receive off-resonance microwaves emitted by the microwave module and apply the off-resonance microwaves to the sample to be detected.
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